1. Field of the Invention
The present invention relates to novel functionalized norbornanyl ester derivatives and/or polymers composition, which are produced by reacting substituted norbornenes with a carboxylic acid. In particular, this invention relates to a novel process for making bicyclic chemical raw material and polymeric material from Diels-Alder adduct, which is easily obtained by reacting diene with dienophile.
The invention specifically provides new functional norbornanyl ester derivative compositions represented by the general Formula-1:

The invention also provides new composition of polymer or oligomer comprising the units of norbornanyl ester type represented by the general Formula-2:

The functional norbornanyl ester derivatives and polymer compositions represented by the Formula-1 and Formula-2 are prepared from norbornenyl derivative by Diels-Alder reaction. The norbornenyl derivative represented by the general Formula-3:

In the Formula-1, Formula-2, Formula-3, R1 is a hydrogen atom, a methyl, or a hydroxymethyl group; R2, R3, R4 and R5 are the same or different from each other and are independently selected from the group consisting of hydrogen; halogen; hydroxyl; acid (—C(O)OH); ester (—C(O)ORa); formate (—OC(O)H); acid halide (—C(O)Z); aldehyde (—C(O)H); ketone (—C(O)Ra); nitro (—NO2); carboxamide (—C(O)NRaRb); amine (—NRaRb); silicone (—SiRaRbRc); cyano (—CN); isocyanate (—NCO); alkoxy (—ORa); phosphonate (—P(O)RaRb); unsubstituted or substituted C1-C100 alkyl group, unsubstituted or substituted C2-C100 alkenyl group, unsubstituted or substituted C2-C100 alkynyl group, unsubstituted or substituted C3-C100 cycloalkyl group, unsubstituted or substituted C6-C100 aryl group, when it is substituted with one or more substituent group the substituent group selected from a carboxyl, hydroxyl, thiol, halogen, ester, amine, amide, imide, isocyanate, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl, siloxy, glycidoxy, heterocyclo, carbonate, carboxylate, and quaternary ammonium; R2, R3 and R4 may be acid anhydride groups (—C(O—O—C(O)—) or imide groups (—C(O)—NRd—C(O)—) formed by being bonded to each other when they are the functional groups; X represents oxygen, CH2, or CH2—CH2; k is an integer of 0 to 100; 1 is an integer 0 to 1; m and n both represent an integer 0 to 5; p is an integer 1 to 1000; Y is a bridge member selected from the group consisting of (—C(O)O—), (—R6—), (—R7C(O)O—), (—C(O)OR7O—), (—C(O)OR7OC(O)—), (—O—), (—OR7O—), (—R7OC(O)OR8—), (—R7C(O)OR8—), and (—R7C(O)R8—); wherein Ra, Rb and Rc are independent hydrocarbyl or substituted hydrocarbyl, Rd is a hydrocarbyl group substituted with hydroxyl, alkoxy, alkenyl, amine, amide or imide group; Z is a halogen atom; R6, R7 and R8 are divalent organic groups selected from substituted or unsubstituted alkanes, alkenes, cycloaliphatic groups, amine and aromatic groups; At least one of the substituents R2, R3, and R4 is a polar functional group containing at least one atom selected from the group consisting of oxygen, nitrogen, phosphorus, sulfur, silicon and boron;
This invention also provides the process of producing the norbornenyl derivative of Formula-3; the norbornanyl ester derivative of Formula-2, the norbornenyl polymer of Formula-2 and a norbornanyl lactone derivative or polymer.
2. Description of the Related Art
Norbornane based alicylic derivatives and polymers have great economic significance as important intermediate or polymeric material for the chemical industry. They are particularly attractive because their bulky, bridged cyclic skeleton affords unique properties such as better adhesion, low density, high rigidity, good surface hardness, high glass transition temperatures, better transparency, heat and chemical resistance, low birefringence, low surface energy, optical clarity, low shrinkage, low moisture absorption, low hygroscopy, and improved crystallinity. These compounds and the resulting polymeric materials are used in various articles ranging from optical materials, low-dielectric IT materials, coating, ink, and medicinal materials to high performance engineering plastics. Accordingly, today, demand in supply of norbornane derivatives or polymers have steadily increased.
However, the application of norbornane cyclic derivatives and polymers depends to a high degree on the availability and price of the bicyclic raw materials. Most bicyclic compounds used in the industry are made from hydrogenation or oxidization of Diels-Alder adducts obtained from dicyclopentadiene (DCPD) and other chemicals.
There are some reports regarding preparation of norbornanyl derivatives and polymers. One method is hydrogenation of the norbornenyl derivative. For example, U.S. Pat. Nos. 4,948,866 and 6,309,719 as well as Japanese patent application 2007022962 reported the catalytic hydrogenation process of preparing alicyclic compounds.
Another method is oxidation of cyclic olefin. U.S. Pat. No. 5,214,125 and 20110257317 claim that alicyclic dicarboxylic acid can be produced by oxidizing a corresponding cyclic olefin and opening its ring with potassium permanganate or nitric acid. U.S. patent 20100094030 reported preparation of alicyclic diepoxides from norbornenyl derivatives with percarboxylic acid.
In U.S. Pat. No. 6,939,997, dimethanolic derivatives of dicyclopentadiene are obtained by hydrogenating TCD-aldehydes, which are the hydroformylation products of dicyclopentadiene.
A polyester possessing a norbornane backbone and exhibiting excellent heat resistance and transparency can be prepared by hydroesterification of methyl formate with norbornene monomer in the presence of catalytic amounts of ruthenium complexes (WO 2012035874).
Dicyclopentadiene monoesters are known. For example, see U.S. Pat. Nos. 7,033,676, 5,252,682. Generally, dicyclopentadiene monoesters are prepared by reacting maleic anhydride with dicyclopentadiene in the presence of water. Dicyclopentadiene maleic monoester can be used for production of unsaturated polyester resins as a chain end capping agent.
Substituted norbornanyl esters can be prepared from hydrocarboxylation reaction. These bicyclic compounds are normally produced by acid-catalyzed addition of the corresponding carboxylic acids to norbornenyl ring in the Diels-Alder adduct to form ester linkages. Many catalysts have been proposed, including metal trifluoromethanesulfonate (U.S. patent 20090012324), activated acidic clay (U.S. Pat. No. 7,557,148), triflic acid (Japanese patent application 2003171346; Macromolecules 2008, 41, 524-526).
Lactone ring containing compounds such as 2,6-norbornane carbolactone-3-carboxylic acid can be prepared from 5-norbornene-2,3-dicarboxylic anhydride with 30% sulfuric acid as disclosed in U.S. Pat. No. 6,517,994.
The known processes for preparing norbornane derivatives by hydrogenation, oxidization, hydroalkoxylation, and hydrocarboxylation all require the presence of specific catalyst systems which are either unavailable in industry or environmentally and economically impractical. Alternatives to hydrogenation and oxidization methods are needed due to technical reasons as well as the supply shortage. However, there has been no report on the efficient preparation of ridged, bicyclic skeleton derivatives or polymers with hydrocarboxylation reaction. There is therefore a need for a simple and inexpensive process for preparing chemical raw materials or polymeric materials containing bridged ring structure. A valuable process would avoid the use of a catalyst.